Dyes from stilbene dicarboxylic acid amides



United States Patent DYES FROM STILBENE DICARBOXYLIC ACID AMIDES Robert s. Long, Bound Bro ok, and; Sien-M. Tsang, Middlesex, N.J., assignors. toAmerican Cyanamid' Comparry, New York, N.Y., a corporation of Maine No Drawing. Original application December 30, 1953,

,SeriaLNo. 401,376. Divided and this application December 16, 1957, Serial No. 702,769

4 Claims. Cl. 260-240) This invention relates to new dyes and, more specifically, it relates to new vat dyes of the structure:

in which Ar is a vattable organic radical. More specifically, Ar may be (1) a vattable organic radical such as anthraquinone, substituted anthraquinones, dianthrimides, anthraquinone acridones, dibenzanthrones, anthrapyrimidones, pyrazoleanthrones, and the like.

Acylarnino derivatives of anthraquinoneshave been used as dyes in the past; Like mostsimple anthraquinone;

derivatives; 4-aminoanthraquinone-l(N), 2-benzacridone 1 and its halogen and alkyl derivatives; 4-amino-1, 1-dianthrimide-Z,2'-carbazole, 5 amino-1,l'-dianthrimide-2,2- carbazole, amino dibenzathrone, 4-amino-1,9-anthrapyrimidone, 4-arnino-1,9-pyrazolanthrone, 4-amino-1,9-isothiozoloanthrone and the like.

The stilbene dicarboxylic acid amides can be prepared by a variety of conventional methods. Thus, the stilbene dicarbloxyl ic acid may be converted to the di-acid chloride by the use of phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, thionyl chloride, or a similar agent. The acid chloride may then be reacted with twosmoles of the amine in the presence of an inert solvent if necessary. A convenient method is to heat the dicarboxylic acid in an excess of thionyl chloride under reflux, to distill oil the excess reagent, and to treat the acid chloride with the amine in pyridine at the boil. Still better, the. dicarboxylic acid is reacted with only the theoret ical; amount of thionyl chloride by gently warming inpyridine, and the amine is then added directly to the reaction mixture, which is then heated at the boiling point. An alternative method whereby one may isolate the acid chloride in pure form is to heat the dicarboxylic acid withthe theoretical amount of thionyl chloride in. an indifferent medium such as nitrobenzene; the. acidchloride precipitates,out,and'rnay.be filtered'ofi; it is then reacted with the amineastbefore.

This application is andivision of our copending appli cation, Serial No. 401,376, filed'Deccmber 30, 1953.

Curt-invention canbe; illustrated by the following examples, in which-parts are by weight unless otherwise specified.

. Example. I

2.7 parts of 4,4'-stilbene dicarbonyl chloride and 4.0 parts of l-aminoanthraquinone are introduced into 72 parts of nitrobenzene and the mass is stirred while being graduallyheated, to 140 C. It is then held at 140-150 C. until thereaction is substantially complete after which thesiurryis cooled., The product is isolated'by filtration and washing with nitrobenzene and alcohol. Thedye is obtained as an orangeeyellow powder which dyes cotton bright golden yellow'shades from a dull violet vat. It dissolvesin concentrated H with an orange-brown color.

Equivalent amounts ofZ-aminoanthraquinone, 4-amino 1,1 dianthrimide;2,Zf-carbazole, 4-amino-1,9-anthrapyri wide tamin :l y az l n hw e or m isot,hiazoloanthrone.,canbesusbtituted :for. the amino an thraquinone to give new vat dyes. i

Example 2 r The procedure of .Example 1 is followed, using an equivalent quantity of 5'-trifluoromethyl-4-aminoanthraquinone-l(N)-2-benzacridone in place of the l-aminoanthraquinone. The product is a blue powder which dyes cotton a blue shade of good properties.

Example 3 0 o 2 The procedure of Example 2 is followed, using an equivalent amount of aminodibenzenzanthrone in place of the aminoanthraquinone. The product so obtained is a 45 green blue solid which dyes cotton fast green blue shades.

We claim: 1. Compounds having the formula:

in which Ar is a vattable organic residue selected from the group consisting of anthraquinone, anthraquinone metatrifluoromethyl benzaeridone, dianthramide carbazole, anthrapyrimidone, pyrazolanthrone and isothiazoloanthrone.

2. A compound having the formula:

Fac

3. A compound having the formula:

4. A compound having the formula:

References Cited in the file of this patent Lubs: Chemistry of Synthetic Dyes and Pigments, ACS Monograph No. 127, pp. 440-441, Reinhold Publishing Corporation, 1955. 

1. COMPOUNDS HAVING THE FORMULA:
 2. A COMPOUND HAVING THE FORMULA: 